Ammonia As A Marine Fuel Safety Handbook
AMMONIA AS A MARINE FUELSAFETY HANDBOOK
TABLE OF CONTENTSExecutive Summary . 3Foreword . 4Participants in the GSP Pilot on Ammonia as Fuel . 51Introduction . 62Ammonia as a fuel . 73452.1Properties of ammonia . 72.2Comparison with methane (LNG) . 8Toxicity . 93.1Health effects . 93.2Environmental effects. 10Regulatory framework. 114.1SOLAS . 114.2The IGF Code . 114.3The IGC Code . 114.4How to advance regulatory framework. 12Design implications of differences between ammonia and methane (LNG). 135.16Safety concept of current regulations in the IGF Code and DNV GL rules for LNG fuel 13General design of ammonia fuelled ships . 156.1Bunkering. 156.2Fuel storage . 166.3Tank connection spaces and fuel preparation rooms. 176.4Fuel supply . 186.5Machinery space . 196.6Hazardous area - flammability and toxicity . 196.7Personnel protection . 226.8Fire safety . 237References . 248The development of the Safety Handbook . 252Ammonia as a Marine Fuel Safety Handbook
Executive SummaryThe technology required to propel and power ships with ammonia as fuel is still immature,and extensive development and policy measures are needed for its use on a larger scale overthe next decade.Effective safety regulations for the use of ammonia as fuel on board ships are currently not inplace and must be established. Ammonia is a toxic chemical and it is important that the additional safety challenges are thoroughly addressed before considering ammonia as a marinefuel.The maritime industry has experience with transport of ammonia cargo in gas carriers andthe use of ammonia as refrigerant. However, the introduction of ammonia as fuel createsnew challenges related to safe ammonia fuel bunkering, storage, supply and consumptionfor different ship types.Current international regulatory framework and maritime industry experience with alternativefuels is mainly related to methane (LNG). A comparison of the properties of ammonia andmethane is made to evaluate whether the safety barriers developed for methane are relevantfor ammonia.Ammonia is less flammable than methane and constitutes a lower, but not ignorable, explosion risk. Due to the toxicity it is still considered essential to be able to control all leakagescenarios in order to design and operate a safe ship. In our view, the safety principles developed for LNG fuel related to segregation, double barriers, leakage detection and automaticisolation of leakages will also be suitable guidance when establishing safety requirements forammonia fuelled ships.On this background, we discuss how the ship arrangement is affected by the ammonia fuelinstallation and in general terms how to accommodate for ammonia fuel in the differentparts of the system. The additional safety barriers and arrangements affects the ship arrangement.This handbook is developed in the Green Shipping Programme (GSP) as a work package on“safety standardization” in the Colorline Pilot on Ammonia as Fuel.3Ammonia as a Marine Fuel Safety Handbook
ForewordShipping faces major challenges adjusting to zero emissions over the next decades.Among the solutions pointed out - both for existing tonnage and newbuilds - we often findammonia.This handbook is an important contribution on the path to the safe and efficient use of ammonia as a marine fuel and assists the industry with practical guidance on how the most important safety barriers associated with ammonia can be solved.The handbook is developed by DNV GL on behalf of the Green Shipping Programme, withinput from the Norwegian Maritime Authority and other partners in the Ammonia Pilot.The Green Shipping Programme is a collaborative project between the authorities and theprivate business community and aims to support increased uptake of environmentallyfriendly solutions for ships. The goal of the programme is for Norway to become a worldleader in environmentally friendly and efficient shipping.AMUND DRØNEN RINGDALDirector National and International Politics Norwegian Shipowners’ AssociationLeader of the Steering Committee, Green Shipping Programme4Ammonia as a Marine Fuel Safety Handbook
Participants in the GSP Pilot on Ammonia as Fuel5Ammonia as a Marine Fuel Safety Handbook
1 IntroductionMany studies have pointed to ammonia (NH3) as a potential fuel for shipping (e.g. MaritimeKnowledge Centre, TNO & TU delft, 2017; OECD, 2018; DNV GL, 2020a).The technology required to propel and power ships with ammonia as fuel is still immature,and extensive development and policy measures are needed for its use on a larger scale overthe next decade.Several engine manufacturers are currently looking into the challenges of burning ammoniain their engines, with the aim of having engines available 3 to 4 years from now. Fuel celltechnology using ammonia as a fuel is also under development. 1,2,3Effective safety regulations for the use of ammonia as fuel on board ships are currently not inplace and must be established. Ammonia is a toxic chemical and it is important that the additional safety challenges are thoroughly addressed before considering ammonia as a marinefuel.The maritime industry has experience with carriage of ammonia in gas carriers and the use ofammonia as refrigerant. However, the introduction of ammonia as fuel creates new challenges related to safe ammonia fuel bunkering, storage, supply and consumption for different ship types.DNV GL has issued a white paper on ammonia as a marine fuel examining the current use ofammonia in shipping and other industries and considering what it would take for ammoniato be adopted at scale as a maritime fuel (DNV GL, 2020b).This handbook is developed in the Green Shipping Programme (GSP) as a work package on“safety standardization” in the Colorline Pilot on Ammonia as Fuel with the intention to provide practical guidance on safety aspects of ship design in the development of ammoniafuelled ships for ship owners, yards and designers.This handbook has the following structure: Chapter 2 – Ammonia as fuel Chapter 3 – Toxicity Chapter 4 – Regulatory framework Chapter 5 – Design implications of differences between ammonia and methane (LNG) Chapter 6 – General design of ammonia fuelled ssion-ammo-nia-fuel-cell-module/6Ammonia as a Marine Fuel Safety Handbook
2 Ammonia as a fuel2.1 Properties of ammoniaThe basic properties of ammonia are summarized and compared with methane in Table 2-1.Under atmospheric temperature and pressure, ammonia is a colourless, toxic gas with asharp and penetrating odour.Ammonia in its pure form is referred to as anhydrous (“without water”) ammonia. Ammoniais hygroscopic, which means it has a high affinity for water.In gaseous form it is lighter than air. However, due to its hygroscopic properties, released anhydrous ammonia will rapidly absorb moisture from air and form a dense and visible whitecloud that may have a higher density than air.Ammonia also dissolves easily in water to form ammonium hydroxide (NH4OH), a caustic solution and weak base.Ammonia has alkaline properties and is corrosive. Ammonia will corrode galvanized metals,cast iron, copper, brass or copper alloys. Hence, careful material selection is required.Ammonia is flammable, but hard to ignite. Outdoors, ammonia vapours will generally notconstitute a fire hazard. Indoors, in confined areas, the risk of ignition will be higher, especially if oil and other combustible materials are present. Pressure vessels used for storage ofammonia may explode when exposed to high heat input.Ammonia is transported in the liquid state; therefore, it must either be compressed or refrigerated or some combination of the two. Fully refrigerated ammonia storage tanks containliquid at -33 C at atmospheric pressure, while fully pressurised tanks are designed for 18 barwhich corresponds to the ammonia vapour pressure at 45 C.7Ammonia as a Marine Fuel Safety Handbook
2.2 Comparison with methane (LNG)Current international regulatory framework and maritime industry experience with alternativefuels is mainly related to methane (LNG). A comparison of the properties of ammonia andmethane is made in Table 2-1. This comparison may be useful when evaluating whether thesafety barriers developed for methane are also relevant for ammonia.Table 2-1 Properties of ammonia compared with methanePropertyAmmonia (NH3)Methane (CH4)Boiling temperature (1 bar)-33 C-162 CVapour pressure (45 C)18 bar345 barGas density0.73 kg/m30.66 kg/m3Flammability range 415-28%5.3–17%Auto ignition temperature651 C537 CMinimum ignition energy8 mJ0.27 mJSolubility in water (at 20 C)531 g/lNoMain ammableFlammableAsphyxiatingCompared with methane, ammonia has a lower, but not ignorable, explosion risk. However, itis a lethal toxin at much smaller concentrations than the flammability range of either methane or ammonia vapours becomes flammable. As opposed to LNG, ammonia is not storedat cryogenic temperatures.4The minimum concentration of a particular combustible gas or vapour necessary to support its combustionin air is defined as the Lower Explosive Limit (LEL). The maximum concentration of a gas or vapor that will burn inair is defined as the Upper Explosive Limit (UEL). Above this level, the mixture is too “rich” to burn. The rangebetween the LEL and UEL is known as the flammable range for that gas or vapour.8Ammonia as a Marine Fuel Safety Handbook
3 Toxicity3.1 Health effectsAmmonia is a toxic substance. Acceptable human exposure limits to ammonia are defined bylegislation and is typically a function of concentrations and exposure time. The limit is set between 25-50 ppm with dangerous consequences for exposure to concentrations above 300ppm (Valera-Medina et al., 2018). Examples of exposure guidance are shown in in Table 3-1and Table 3-2.Table 3-1 Exposure guidance (Karabeyoglu A, Brian E., 2012)EffectAmmonia concentration in air (by volume)Readily detectable odour20 – 50 ppmNo impairment of health for prolonged exposure50 – 100 ppmSevere irritation of eyes, ears, nose and throat.No lasting effect on short exposure400 – 700 ppmDangerous, less than ½ hours exposure may be fatal2000 – 3000 ppmSerious edema, strangulation, asphyxia, rapidly fatal5000-10000 ppmBased on Acute Exposure Guideline Levels (AEGL) for airborne chemicals defined by the Environmental Protection Agency (EPA) US, the limits to ammonia exposure can be identified asshown in Table 3-2.Table 3-2 EPA Acute Exposure Guideline Levels (EPA, 2016)Ammonia 7664-41-7 Expressed in ppm10 min30 min60 min4h8hAEGL 13030303030AEGL 2220220160110110AEGL 3270016001100550390AEGL 1: Notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effectsare not disabling and are transient and reversible upon cessation of exposure.AEGL 2: Irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape.AEGL 3: Life-threatening health effects or death.Anhydrous ammonia is a hydroscopic compound, which means that it seeks water from thenearest source, including the human body. This places the eyes, lungs, and skin at greatest9Ammonia as a Marine Fuel Safety Handbook
risk because of their high moisture content. Caustic burns result when the anhydrous ammonia dissolves into body tissue.An additional concern is the low boiling point of anhydrous ammonia. The chemical freezeson skin contact at room temperature. It will cause burns similar to, but more severe than,those caused by dry ice (Schwab, Charles V. et al., 1993).Most deaths from anhydrous ammonia are caused by severe damage to the throat and lungsfrom a direct blast to the face. When large amounts are inhaled, the throat swells shut, andvictims suffocate. Exposure to vapours or liquid also can cause blindness.Combustion of ammonia may form toxic nitrogen oxides. It is recognised that NO2 fromother sources can aggravate cardiovascular and respiratory diseases, with an estimate of23,500 premature deaths per year only in the UK alone. Although considerable research hasbeen conducted understanding the formation process of this pollutant, its formation andconsumption during combustion and post-combustion processes using ammonia are still atthe core of the research agendas of various research groups (Valera-Medina et al., 2018).3.2 Environmental effectsFrom a safety point of view, drainage of ammonia spills overboard and discharge of ammonia vapour underwater is preferable to keeping ammonia onboard. However, release of ammonia to the sea has impact on the environment. Ammonia is classified as toxic to aquaticlife with long lasting effects according to GHS 5.Combustion of ammonia in internal combustion engines may generate NOx and also N2Owhich is a powerful greenhouse gas. It is assumed that existing SCR technology is capable ofhandling the NOx problem, and that engine manufacturers will need to find solutions tohandle N2O if ammonia is going to be a viable zero emission fuel.5Globally Harmonized System of Classification and Labelling of Chemicals (GHS). United Nations, New York andGeneva, 2011. ubli/ghs/ghs rev04/English/ST-SG-AC10-30-Rev4e.pdf10Ammonia as a Marine Fuel Safety Handbook
4 Regulatory framework4.1 SOLASThe use of fuels is regulated by the International Maritime Organization (IMO) through theInternational Convention for the Safety of Life at Sea (SOLAS). The regulations for conventional fuel oils are prescriptive and based on decades of experience. Utilizing fuels with aflashpoint below 60 C (defined as Low Flashpoint Fuels) has generally been prohibited toprevent tank explosions and fires.In 2015, the SOLAS Convention was amended to allow the use of low flashpoint fuels forships complying with the International Code of Safety for Ships Using Gases or Other LowFlashpoint Fuels (IGF Code).4.2 The IGF CodeThe IGF Code provides an international standard for the safety of ships using low-flashpointfuel, other than gas carriers which have to comply with separate requirements in the IGCCode (see 4.3).The IGF Code requires that the safety, reliability and dependability of the systems shall beequivalent to that achieved by new and comparable conventional oil-fuelled main and auxiliary machinery.The IGF Code specifies a set of functional requirements applicable for all fuel types coveredby the Code, but only contains specific design requirements to LNG. Specific design requirements for other low-flashpoint fuels (like e.g. ammonia) will be added as, and when, they aredeveloped by the Organization.Until such regulations are in place, approval of ships using other fuels than LNG will be basedon first-principle analysis demonstrating that the design complies with the basic functionalrequirements of the IGF Code. This risk-based approval process is referred to as the ‘alternative design’ approach, where an equivalent level of safety needs to be demonstrated.The alternative design approach can be a time-consuming process with a high degree of uncertainty and therefore potentially higher business risk than the prescriptive experiencebased rules that the maritime industry is used to working with. This must be considered as abarrier against uptake of alternative fuels in the industry.4.3 The IGC CodeThe IGC Code provides an international standard for the safe carriage by sea in bulk of liquefied gases.The IGC Code includes a separate chapter on the use of cargo as fuel but does not permitthe use of cargoes identified as toxic products like ammonia for this purpose. This meansthat the Code, in its current form, does not permit gas tankers to use ammonia as a fuel.11Ammonia as a Marine Fuel Safety Handbook
Ammonia is transported as cargo in large quantities in gas carriers. The requirements in theIGC Code can therefore provide useful guidance in how to design fuel storage systems forammonia.4.4 How to advance regulatory frameworkClassification Societies tend to have a faster rule development cycle than IMO. When a Classification Society has developed a set of rules covering the use of a fuel where specific design requirements are not included in the IGF Code, a Flag Administration may accept theapplication of this rule set to ease the alternative design approach. A set of class rules mayalso form basis for development of international regulations in IMO.12Ammonia as a Marine Fuel Safety Handbook
5 Design implications of differences between ammonia andmethane (LNG)Most alternative fuels have chemical and physical properties which generate more severesafety challenges and requires a more complex fuel containment system than conventionalfuel oils. Additional safety barriers are required to maintain the safety level. Each alternativefuel has its unique properties and associated hazards requiring special consideration.Both anhydrous ammonia and methane are gases with a boiling temperature which is notcompatible with conventional storage tanks onboard ships. Consequently, both gases need astorage and supply system that can manage the pressure increase and boil-off gas that isgenerated by heat input to the system.The low boiling temperature of methane (-163 C at atmospheric conditions) introduces a design challenge with respect to selection of materials to ensure ductility at low temperatures.This can also be an issue for ammonia (-33 C at atmospheric conditions) but can be overcome with less sophisticated material selections. On the other hand, for ammonia the corrosive properties require special consideration in the choice of materials.Due to the high flammability and low minimum ignition energy of methane, it is essential toprevent leakages from the fuel storage and supply system. Ignition of leaking methane in enclosed spaces may result in explosions with severe consequences for the ship and personsonboard. Ammonia is less flammable than methane and constitutes a lower explosion risk.5.1Safety concept of current regulations in the IGF Code and DNV GLrules for LNG fuelThe existing DNV GL rules for LNG fuel cover the specific design requirements in the IGFCode. Both the IGF Code and the class rules mainly focus on managing different leakage scenarios and as indicated in Figure 5-1, the essential safety barriers are related to:13 Segregation; keeping the installation away from areas where it may be damaged bycollision or grounding, external fires, cargo handling or other ship operations. Double barriers; arrangements that allows leakages from the fuel system to be managed safely. This will typically be to provide a secondary barrier around any leakagepoint. In practice, such barriers consist of specially designed spaces (e.g. tank connection spaces, fuel preparation rooms) and double piping arrangements. Leakage detection; systems that can detect leakages of gases and liquids from thefuel system. The detection methods are dependent on arrangements, but normallyincludes gas detection systems, low temperature measurements, changes in pressureand temperature. Automatic isolation of leakages; systems and arrangements that can isolate theleakage from the leakage source when the detection systems above find somethingwrong with the fuel system. In order to achieve this, a number of isolation devices arerequired in the system enabling automatic shut-down of the fuel supply to the damaged system.Ammonia as a Marine Fuel Safety Handbook
SegregationProtect fuel installationfrom external eventsLeakage detectionDouble barriersProtect shipagainst leakagesAutomatic isolation of leakagesGive warning and enableReduce consequenceautomatic safety actionsof a leakageFigure 5-1 Safety concept of the current regulations in the IGF Code and DNV GL rulesfor LNG fuel.In our view, the safety principles described above will also be suitable guidance when establishing safety requirements for ammonia fuelled ships:14 Segregation; keeping the installation away from areas where it may be mechanicallydamaged is equally important for ammonia. Double barriers; arrangements that allows leakages from the fuel system to be managed safely is also essential for ammonia due to toxicity and explosion risk. Leakage detection; systems that can detect leakages of gases and liquids from thefuel system is even more important when ammonia is used as a fuel since it is a lethaltoxin at low concentrations. Automatic isolation of leakages; as for the leakage detection above it will be important to limit the amount of ammonia in a leakage scenario.Ammonia as a Marine Fuel Safety Handbook
6 General design of ammonia fuelled shipsIn this chapter we discuss how the ship arrangement is affected by the ammonia fuel installation and in general terms how to accommodate for ammonia fuel in the different parts of thesystem.The different parts of an ammonia fuel installation are illustrated in Figure 6-1. The additionalsafety barriers and arrangements affects the ship arrangement.Figure 6-1 Principle diagram ammonia fuelled installation (DNV GL).6.1 BunkeringFocus area: Reduce the risk of ammonia leakages during bunkering and limit risk andconsequences of exposure to ammonia for personnel involved in the bunkering operations.The bunkering operation with its handling, connection and disconnection of heavy bunkeringhoses is subjecting the personnel involved to the risk of being directly exposed to ammonia.In order to reduce the risk of leakages, the lay-out of the bunkering station should enable asmooth bunkering procedure by providing ample space for the necessary operational stepswith lifting equipment supporting the mounting of heavy bunkering hoses. Bunkering hosesshould be equipped with dry-disconnect couplings and break-away devices that will preventoverstressing hoses and manifold in case of a drift-off scenario.To limit the exposure time, the bunkering control station should preferably be in a safe location enabling the crew to remotely oversee the bunkering operation.15Ammonia as a Marine Fuel Safety Handbook
The bunkering lines onboard should be arranged in such a way that it is possible to drain theammonia to the storage tank and the bunkering hose back to the bunkering facility. The shipbunkering line should be purged with inert gas after fuelling operations to eliminate the riskof ammonia leakages when it is not in use.Development of proper bunkering procedures including communication with the bunkersupplier and training of crew is also considered essential to refuel safely.It is recognized that the risk of ammonia exposure cannot be eliminated by good design andproper operating procedures.Therefore, people involved in the bunkering operations should be equipped with PersonalProtective Equipment (PPE) to protect them from exposure to anhydrous ammonia. The PPEshould consist of large aprons, special gloves with long sleeves, suitable footwear, coverallsof chemical-resistant material, and tight-fitting goggles or face shields or both. The protective clothing and equipment should cover all skin so that no part of the body is unprotected.If a person is exposed to anhydrous ammonia, showering the contaminated areas with ampleamounts of water is the best first aid treatment. For this purpose, emergency showers andeyewashes should be provided in convenient locations outside the bunkering station.There are several other design features which may reduce the consequence of a leakage during bunkering: proper mechanical shielding of all leakage points on the bunkering manifold including temporary mechanical shielding of the bunkering connection leakage detection with automatic closing of bunker valve water spray system above the bunkering manifold to reduce toxic vapours in thebunkering station spill tray below the bunkering manifold to collect any leakage and to drain the water/ammonia overboard manual emergency stop a ship-shore link (SSL) or an equivalent means for automatic and manual ESD communication to the bunkering source.6.2Fuel storageFocus area: Storage of ammonia without vapour release to the atmosphere.Ammonia is transported in the liquid state; therefore, it must either be compressed or refrigerated or some combination of the two. Fully refrigerated ammonia storage tanks containliquid at -33 C at atmospheric pressure, while fully pressurised tanks are designed for 18 barwhich corresponds to the ammonia vapour pressure at 45 C.In principle, tank types accepted for cargo carriage in the IGC Code will also be accepted asfuel tanks. In practice type A (fully refrigerated) and C (semi- or fully pressurized) tanks asdefined in the IGC code are used for transport of ammonia cargo in gas carriers.16Ammonia as a Marine Fuel Safety Handbook
There are several safety related factors to consider when choosing type of fuel tank: Venting of tank vapours should be prevented at all times. This implies that tanks forammonia will need a boil-off gas (BOG) management system unless they are designed for the full vapour pressure of ammonia at ambient temperatures (18 bar). For tanks requiring secondary barriers, management of leakage scenarios and thesubsequent emergency venting of fuel gases must be specially considered. The choice of fuel tank may also impact flexibility with regard to compatibility withbunkering facilities with respect to pressure and temperature.Due to the corrosivity of ammonia, special requirements in the IGC Code for materials usedin ammonia storage tanks and associated systems should be observed.Focus area: Protect the ammonia fuel installation from external events that could damage the tank causing accidental release of ammonia.To reduce the risk of accidental release of ammonia, the tank location should be carefullyconsidered with respect to any external events that could potentially damage the tank.For collision and grounding protection, the requirements defined in the IGF Code for LNGtanks and piping are considered relevant.Ammonia tanks should preferably be located away from exposure to ship and cargo operations. Alternatively, appropriate mechanical protection should be considered.6.3Tank connection spaces and fuel preparation roomsFocus area: Safely contain leakages to prevent leaking ammonia from spreading toother areas onboard.Tank connection spaces (TCS) and fuel preparation rooms (FPR) should be arranged to provide a secondary barrier against ammonia leakages in areas where a double pipe protectionis not practical to arrange. All tank conn
2 Ammonia as a fuel . 2.1 Properties of ammonia . The basic properties of ammonia are summarized and compared with methane in . Table 2-1. Under atmospheric temperature and pressure, ammonia is a colourless, toxic gas with a sharp and penetrating odour. Ammonia in its pure form is referred to as anhydrous (“without water”) ammonia. Ammonia
Ammonia is typically created by combining nitrogen with hydrogen. Therefore, the emissions from producing hydrogen as feedstock and the emissions arising from the synthesis of ammonia should be considered as part of the life cycle emissions of ammonia fuel. Table 1 shows the well-to-tank emissions for ammonia production, transmission,
Ammonia: An Essential Chemical Ammonia is a naturally occurring chemical in the atmosphere, as well as an essential man-made chemical. It is represented by the chemical formula nH 3. Ammonia in this form is also known as ammonia gas or anhydrous (“without water”) ammonia. At room temperature, amm
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Ammonia Discharge [2013 ANSI/ASHRAE §9.7.8.2] o Ammonia Discharge. Ammonia from pressure relief valves shall be discharged into one or more of the following: a. The atmosphere, per Section 9.7.8 b. A tank containing one gallon of water for each pound of ammonia that will be released in one hour from the largest relief
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The REST API cannot accept more than 10 MB of data. Audience and Purpose of This Guide The primary audience for this manual is systems integrators who intend to enable configuration and management of the system features through integrated systems. This manual is not intended for end users. Related Poly and Partner Resources See the following sites for information related to this release. The .
